Adsorbent material, adsorbent sheet, separation membrane, artificial dialysis machine, and production method

JPWO2023204279A5Inactive Publication Date: 2025-01-07
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Patent Information

Application Number
JP2024516314
Authority / Receiving Office
JP · JP
Patent Type
Applications
Priority Date
2023-04-20
Filing Date
2023-04-20
Publication Date
2025-01-07
Estimated Expiration
Not applicable · inactive patent

AI Technical Summary

Technical Problem

Current adsorbents used in hemodialysis, such as those described in Non-Patent Document 1, have limited capacity to adsorb a wide range of disease-causing substances, which can lead to incomplete removal of toxins from the blood in patients with kidney disease, resulting in persistent health issues like uremia and electrolyte imbalances.

Method used

Development of an adsorbent comprising two-dimensional MXene particles with a specific composition formula MₘXₙ, where M is a group 3, 4, 5, 6, or 7 metal, X is a carbon or nitrogen atom, and n is between 1 and 4, with surface modifications, allowing for the adsorption of a broader spectrum of adsorbates, including proteins and electrolytes, through their charged sites and edge interactions.

Benefits of technology

The MXene-based adsorbent effectively adsorbs a wider variety of disease-causing substances, including proteins and electrolytes, improving the efficiency of toxin removal from blood, thereby mitigating symptoms associated with kidney disease and inflammatory conditions.

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Abstract

One of the objectives of the present disclosure is to provide a novel adsorbent material to be used for adsorbing a wider range of adsorbates in comparison with non-patent document 1. Another objective of the present disclosure is to provide an adsorbent sheet, a separation membrane, an artificial dialysis machine that use such absorbent material, and a production method thereof. This adsorbent material is to be used for adsorbing disease causative substances and comprises secondary particles having one or more layers, Each layer comprises: a layer body represented by the formula MmXn (where M is at least one group 3, 4, 5, 6, or 7 metal; X is a carbon atom, a nitrogen atom, or a combination thereof; n is 1 to 4 inclusive; and m is greater than n but no greater than 5); and a modification or a terminal T present on the surface of the layer body (T is at least one selected from the group consisting of a hydroxyl group, a fluorine atom, a chlorine atom, an oxygen atom, and a hydrogen atom).
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Description

Adsorbent, adsorption sheet, separation membrane, artificial dialysis device and manufacturing method

[0001] The present disclosure relates to an adsorbent, an adsorbent sheet, a separation membrane, an artificial dialysis machine, and a manufacturing method thereof.

[0002] The number of patients with kidney disease is increasing year by year, and according to statistics from the Japanese Society for Dialysis Therapy, the number of chronic dialysis patients increased by approximately 17% between 2010 and 2020. When kidney function declines due to kidney disease, disease-causing substances accumulate in the blood, which can result in uremia, electrolyte metabolism disorders, autoimmune diseases, etc. To treat the various symptoms associated with kidney disease, hemodialysis-type kidney function substitutes are used, which remove disease-causing substances from the body.

[0003] Non-Patent Document 1 describes an adsorption-type blood purifier that uses cellulose beads with cetylamine immobilized thereon as an adsorbent as a filter used in a hemodialysis-type kidney function substitute.

[0004] Medical Device Package Insert "Rixel", Kaneka Corporation, revised January 2017 (10th edition)

[0005] The adsorbent described in Non-Patent Document 1 is limited in the types of adsorbates.

[0006] One of the objects of the present disclosure is to provide a novel adsorbent that can be used to adsorb a wider range of adsorbates than that described in Non-Patent Document 1. Another object of the present disclosure is to provide an adsorption sheet, a separation membrane, an artificial dialysis machine, and a method for producing such an adsorbent that use such an adsorbent.

[0007] The adsorbent material of the present disclosure comprises two-dimensional particles having one or more layers, wherein the layers are represented by the following formula: M m X n(wherein M is at least one metal of Group 3, 4, 5, 6 or 7; X is a carbon atom, a nitrogen atom or a combination thereof; n is 1 or more and 4 or less; and m is greater than n and 5 or less), and a modified or terminated T (T is at least one selected from the group consisting of a hydroxyl group, a fluorine atom, a chlorine atom, an oxygen atom and a hydrogen atom) present on the surface of the layer body, and is used to adsorb disease-causing substances.

[0008] According to the present disclosure, it is possible to provide a novel adsorbent that can be used to adsorb a wider range of adsorbates than Non-Patent Document 1. The present disclosure can also provide an adsorbent sheet, a separation membrane, and an artificial dialysis machine that use an adsorbent that can adsorb a wider range of adsorbates than Non-Patent Document 1, as well as a method for producing such an adsorbent.

[0009] 1 is a schematic cross-sectional view showing two-dimensional particles, which are layered materials that can be used in the adsorbent of the present invention, where (a) shows single-layer MXene and (b) shows multi-layer (exemplarily two-layer) MXene. 2 is a diagram showing a schematic example of an artificial dialysis device using the adsorbent of the present invention. 3 is a diagram showing a schematic example of another artificial dialysis device using the adsorbent of the present invention.

[0010] (Embodiment 1: Adsorbent) The adsorbent of the present disclosure is used to adsorb disease-causing substances and includes two-dimensional particles having one or more layers, the layers having the following composition formula: M m X n (wherein M is at least one metal of Group 3, 4, 5, 6 or 7; X is a carbon atom, a nitrogen atom or a combination thereof; n is 1 or more and 4 or less; and m is greater than n and 5 or less), and a modified or terminated T (T is at least one selected from the group consisting of a hydroxyl group, a fluorine atom, a chlorine atom, an oxygen atom and a hydrogen atom) present on the surface of the layer body.

[0011] According to the present disclosure, it is possible to provide an adsorbent capable of adsorbing a variety of adsorbates, and in particular, it is possible to provide an adsorbent capable of adsorbing disease-causing substances. Although the present disclosure should not be interpreted as being limited to a particular theory, the reason why the adsorbent of the present disclosure is able to adsorb a variety of adsorbates is thought to be as follows.

[0012] That is, the two-dimensional particles contained in the adsorbent of the present disclosure are particles of layered material also called MXene, m X n The surface of the layer body represented by the formula (I) has one or more modified or terminated T (where T is at least one selected from the group consisting of a hydroxyl group, a fluorine atom, a chlorine atom, an oxygen atom, and a hydrogen atom). With this configuration, the layer contained in the two-dimensional particle has charged sites, and the layer surface of the two-dimensional particle is usually negatively charged. Furthermore, the edge faces of the two-dimensional particle (the periphery of the layer of the two-dimensional particle) are usually positively charged. Therefore, when viewed as a whole two-dimensional particle, positively charged adsorbates (e.g., cations, etc.) tend to be adsorbed between the layers, and negatively charged adsorbates (e.g., anions, etc.) tend to be adsorbed on the edge faces of the layers.

[0013] The inventors of the present disclosure have investigated the adsorbates that can be adsorbed by the two-dimensional particles and have found that, in addition to the positively or negatively charged adsorbates, the two-dimensional particles can also adsorb relatively high molecular weight compounds such as proteins.

[0014] The two-dimensional particles can be understood as layered materials or layered compounds, and are referred to as "M m X n T s ", where s is any number, and conventionally, x or z may be used instead of s. Typically, n can be 1, 2, 3, or 4, but is not limited thereto.

[0015] In the present disclosure, the layer may be referred to as an MXene layer, and the two-dimensional particles may be referred to as MXene two-dimensional particles or MXene particles. In the formula for MXene, M is at least one selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and Mn, preferably containing at least Ti, and more preferably at least one selected from the group consisting of Ti, V, Cr, and Mo, and containing at least Ti.

[0016] The proportion of Ti atoms in M ​​may be preferably 50 atomic % or more and 100 atomic % or less, more preferably 70 atomic % or more and 100 atomic % or less, and even more preferably 90 atomic % or more and 100 atomic % or less.

[0017] MXene is a compound represented by the formula: M m X n However, it is known that it can be expressed as follows: Sc 2 C, Ti 2 C, Ti 2 N, Zr 2 C, Zr 2 N, Hf 2 C, Hf 2 N.V. 2 C.V. 2 N, Nb 2 C, Ta 2 C, Cr 2 C, Cr 2 N, Mo 2 C, Mo 1.3 C, Cr 1.3 C, (Ti, V) 2 C, (Ti, Nb) 2 C.W. 2 C.W. 1.3 C, Mo 2 N, Nb 1.3 C, Mo 1.3 Y 0.6 C (in the above formula, "1.3" and "0.6" mean approximately 1.3 (= 4 / 3) and approximately 0.6 (= 2 / 3), respectively), Ti 3 C 2 , Ti 3 N 2 , Ti 3 (CN), Zr 3 C 2 , (Ti, V)3 C 2 、(Ti 2 Nb)C 2 、(Ti 2 Ta)C 2 、(Ti 2 Mn)C 2 、Hf 3 C 2 、(Hf 2 V)C 2 、(Hf 2 Mn)C 2 、(V 2 Ti)C 2 、(Cr 2 Ti)C 2 、(Cr 2 V)C 2 、(Cr 2 Nb)C 2 、(Cr 2 Ta)C 2 、(Mo 2 Sc)C 2 、(Mo 2 Ti)C 2 、(Mo 2 Zr)C 2 、(Mo 2 Hf)C 2 、(Mo 2 V)C 2 、(Mo 2 Nb)C 2 、(Mo 2 Ta)C 2 、(W 2 Ti)C 2 、(W 2 Zr)C 2 、(W 2 Hf)C 2 、 Ti 4 N 3 、V 4 C 3 、Nb 4 C 3 、Ta 4 C 3 、(Ti,Nb) 4 C 3 、(Nb,Zr) 4 C 3 、(Ti 2 Nb 2 )C 3 、(Ti 2 Ta 2 )C3 , (V 2 Ti 2 ) C 3 , (V 2 Nb 2 ) C 3 , (V 2 Ta 2 ) C 3 , (Nb 2 Ta 2 ) C 3 , (Cr 2 Ti 2 ) C 3 , (Cr 2 V 2 ) C 3 , (Cr 2 Nb 2 ) C 3 , (Cr 2 Ta 2 ) C 3 , (Mo 2 Ti 2 ) C 3 , (Mo 2 Zr 2 ) C 3 , (Mo 2 Hf 2 ) C 3 , (Mo 2 V 2 ) C 3 , (Mo 2 Nb 2 ) C 3 , (Mo 2 Ta 2 ) C 3 , (W 2 Ti 2 ) C 3 , (W 2 Zr 2 ) C 3 , (W 2 Hf 2 ) C 3 , (Mo 2.7 V 1.3 ) C 3 (In the above formula, "2.7" and "1.3" mean approximately 2.7 (= 8 / 3) and approximately 1.3 (= 4 / 3), respectively.)

[0018] Typically, in the above formula, M may contain Ti and X may be a carbon atom or a nitrogen atom, and preferably M may be Ti and X may be a carbon atom. For example, the MAX phase may contain Ti 3 AlC 2 and MXene is Ti 3 C 2 T s (in other words, M is Ti, X is C, n is 2, and m is 3).

[0019] In the present disclosure, MXene may contain a relatively small amount of A atoms derived from the MAX phase of the precursor, for example, 10% by mass or less of the original A atoms. The residual amount of A atoms may be preferably 8% by mass or less, more preferably 6% by mass or less. However, even if the residual amount of A atoms exceeds 10% by mass, this may not be a problem depending on the application and use conditions of the two-dimensional particles.

[0020] The two-dimensional particle is an aggregate including one layer of MXene particles (hereinafter simply referred to as "MXene particles") 10a (single-layer MXene particles) as shown in Fig. 1(a). More specifically, the MXene particles 10a are m X n The layer body (M m X n The MXene layer 7a has a main layer 1a and modifications or terminations T3a, 5a present on the surface of the main layer 1a (more specifically, on at least one of the two opposing surfaces of each layer). m X n T s ", where s is an arbitrary number.

[0021] The two-dimensional particles may contain one or more layers. Examples of multi-layered MXene particles (multilayered MXene particles) include, but are not limited to, two-layered MXene particles 10b, as shown schematically in FIG. 1(b). 1b, 3b, 5b, and 7b in FIG. 1(b) are the same as 1a, 3a, 5a, and 7a in FIG. 1(a). Two adjacent MXene layers (e.g., 7a and 7b) in a multilayered MXene particle do not necessarily need to be completely separated and may be partially in contact. The MXene particle 10a may be a mixture of the single-layered MXene particles 10a and the multilayered MXene particles 10b, with some unseparated multilayered MXene particles 10b remaining.

[0022] Although not limiting this embodiment, the thickness of each layer (corresponding to the above-mentioned MXene layers 7a and 7b) contained in the MXene particle can be, for example, 0.8 nm to 5 nm, particularly 0.8 nm to 3 nm (this can vary mainly depending on the number of M atomic layers contained in each layer). The interlayer distance (or gap dimension, shown as Δd in FIG. 1(b)) for each stack of the multilayer MXene particle can be, for example, 0.8 nm to 10 nm, particularly 0.8 nm to 5 nm, more particularly about 1 nm, and the total number of layers can be 2 to 20,000.

[0023] In one embodiment, the ratio of (average major axis length of the two-dimensional surfaces of the two-dimensional particles) / (average thickness length of the two-dimensional particles) is 1.2 or more, preferably 1.5 or more, and more preferably 2 or more. The average major axis length of the two-dimensional surfaces of the two-dimensional particles and the average thickness length of the two-dimensional particles may be determined by the method described below.

[0024] In one aspect, the two-dimensional particles of this embodiment preferably include multilayer MXene particles having a small number of layers obtained through a delamination process. The term "small number of layers" refers to, for example, six or fewer MXene layers. Furthermore, the thickness of the multilayer MXene particles having a small number of layers in the stacking direction is preferably 15 nm or less, more preferably 10 nm or less. Hereinafter, these "multilayer MXene particles having a small number of layers" may be referred to as "small-layer MXene particles." Furthermore, single-layer MXene particles and small-layer MXene particles may be collectively referred to as "single-layer / small-layer MXene particles." The inclusion of single-layer / small-layer MXene particles can enhance the conductivity of the resulting film.

[0025] In multilayer MXene particles with a small number of layers, the ratio of (average major axis of the two-dimensional surface of the two-dimensional particle) to (average thickness of the two-dimensional particle) is 1.2 or more, preferably 1.5 to 10, and more preferably 2 to 5. Hereinafter, these "MXene particles with a small number of layers" may be referred to as "few-layered MXene particles." Furthermore, single-layered MXene particles and few-layered MXene particles may be collectively referred to as "single-layered / few-layered MXene particles." This may improve the film-forming properties of films containing the two-dimensional particles. Examples of the single-layered / few-layered MXene particles include two-dimensional particles obtained through a delamination process.

[0026] In one aspect, the two-dimensional particles of this embodiment preferably contain single-layer MXene particles and few-layer MXene particles, i.e., single-layer and few-layer MXene particles. The proportion of single-layer and few-layer MXene particles with a thickness of 15 nm or less in the two-dimensional particles of this embodiment is preferably 90% by volume or more, more preferably 95% by volume or more. This can improve the film-forming properties of films containing the two-dimensional particles.

[0027] (Average value of major axes of two-dimensional surfaces of two-dimensional particles) The average value of major axes of two-dimensional surfaces of the two-dimensional particles of this embodiment is 0.01 μm or more and 20 μm or less. Hereinafter, the average value of major axes of the two-dimensional surfaces may be referred to as the "average flake size".

[0028] The larger the average flake size, the better the orientation of the two-dimensional particles in the material containing the two-dimensional particles. The orientation of the two-dimensional particles can be evaluated, for example, by the electrical conductivity of the material containing the two-dimensional particles. The average value of the major axis of the two-dimensional surface is preferably 0.02 μm or more, more preferably 0.05 μm or more. When MXene is delaminated by subjecting it to ultrasonic treatment, the majority of the MXene is reduced in diameter to approximately several hundred nanometers in major axis, and therefore the film formed from the single-layer MXene delaminated by ultrasonic treatment is thought to have low orientation of the two-dimensional particles.

[0029] The average value of the major axis of the two-dimensional surface is 20 μm or less, preferably 15 μm or less, and more preferably 10 μm or less, from the viewpoint of dispersibility in the dispersion medium.

[0030] The longest diameter of the two-dimensional plane refers to the longest diameter when each MXene particle is approximated to an ellipse in an electron microscope photograph, and the average longest diameter of the two-dimensional plane refers to the number average of the longest diameters of 80 or more particles. As the electron microscope, a scanning electron microscope (SEM) or a transmission electron microscope (TEM) can be used.

[0031] The average major axis of the two-dimensional particles of this embodiment may be measured by dissolving a material containing the two-dimensional particles in a solvent and dispersing the two-dimensional particles in the solvent, or by measuring the average major axis from an SEM image of the material.

[0032] (Average Thickness of Two-Dimensional Particles) The average thickness of the two-dimensional particles of this embodiment is preferably 1 nm or more and 15 nm or less. The thickness is preferably 10 nm or less, more preferably 7 nm or less, and even more preferably 5 nm or less. On the other hand, considering the thickness of the monolayer MXene particles, the lower limit of the thickness of the two-dimensional particles can be 1 nm.

[0033] The average thickness of the two-dimensional particles is determined as a number-average size (for example, a number-average of at least 40 particles) based on atomic force microscope (AFM) or transmission electron microscope (TEM) photographs.

[0034] The method for producing the two-dimensional particles will be described in detail below, but the present invention is not limited to this embodiment.

[0035] The method for producing the two-dimensional particles includes: (a) preparing a predetermined precursor; (b) removing at least a portion of A atoms from the precursor using an etching solution to obtain an etched product; and (c) washing the etched product to obtain an etched-washed product, and may further include: (d) mixing the etched-washed product with a metal compound containing a metal cation to obtain an intercalation product in which the metal cation is intercalated into the etched-washed product; and (e) stirring the intercalation product to obtain a delamination product in which the intercalation product is delaminated.

[0036] In one embodiment, the above-mentioned etched product or delamination processed product can be used as the two-dimensional particles, and preferably the above-mentioned etched and washed product can be used as the two-dimensional particles.

[0037] Each step will be described in detail below.

[0038] Step (a) First, a predetermined precursor is prepared. The predetermined precursor that can be used in this embodiment is a MAX phase, which is a precursor of MXene, and is represented by the following formula: M m AX n (wherein M is at least one metal of Groups 3, 4, 5, 6, and 7, including at least Ti; X is a carbon atom, a nitrogen atom, or a combination thereof; A is at least one element of Groups 12, 13, 14, 15, and 16; n is 1 or more and 4 or less; and m is greater than n and 5 or less).

[0039] The above M, X, n and m are as described above.

[0040] A is at least one Group 12, 13, 14, 15, or 16 element, and is usually a Group A element, typically Group IIIA or Group IVA, and more particularly may include at least one element selected from the group consisting of Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, S, and Cd, and is preferably Al.

[0041] The MAX phase is M m X n (each X may have a crystal lattice in which it is located in an octahedral array of M) and a layer composed of A atoms is located between them. In the MAX phase, typically when m=n+1, one layer of X atoms is arranged between each of the n+1 layers of M atoms (these are collectively referred to as "M m X n The repeating unit has a layer of A atoms (also referred to as an "A atom layer") arranged as the next layer after the n+1th layer of M atoms, but is not limited thereto.

[0042] The MAX phase can be produced by a known method. For example, TiC powder, Ti powder, and Al powder are mixed in a ball mill, and the resulting mixed powder is sintered in an Ar atmosphere to obtain a sintered body (a block of the MAX phase). The sintered body is then pulverized with an end mill to obtain the powdered MAX phase for the next step.

[0043] Step (b) In step (b), the M of the precursor is removed using an etching solution. m AX n An etching treatment is performed to remove at least a part of the A atoms from the precursor by etching. m X n The treated product is obtained in which at least a part of the layer constituted by A atoms has been removed while the layer represented by the formula (I) is maintained.

[0044] The etching solution may contain an acid such as HF, HCl, HBr, HI, sulfuric acid, phosphoric acid, or nitric acid, and typically, an etching solution containing F atoms can be used. Examples of such etching solutions include a mixture of LiF and hydrochloric acid, a mixture of hydrofluoric acid and hydrochloric acid, and a mixture containing hydrofluoric acid, and these mixtures may further contain phosphoric acid or the like. Typically, the etching solution may be an aqueous solution.

[0045] The etching procedure and other conditions using the above etching solution may be those conventionally used.

[0046] Step (c) In step (c), the treated product obtained by the etching treatment is washed to obtain an etching-washed product. By performing washing, the acid used in the etching treatment and the like can be sufficiently removed.

[0047] The cleaning can be performed using a cleaning solution, typically by mixing the etched material with the cleaning solution. Such a cleaning solution typically contains water, preferably pure water. Alternatively, a small amount of hydrochloric acid or the like may be further contained in addition to pure water. The amount of cleaning solution to be mixed with the etched material and the method for mixing the etched material with the cleaning solution are not particularly limited. For example, such a mixing method may involve coexisting the etched material with the cleaning solution and then stirring, centrifuging, or the like. Examples of the stirring method include stirring using a hand shake, an automatic shaker, a shear mixer, a pot mill, or the like. The degree of stirring, such as the stirring speed and stirring time, may be adjusted depending on the amount and concentration of the etched material to be treated. Washing with the above cleaning solution may be performed one or more times, and it is preferable to perform washing with the cleaning solution multiple times. Specifically, for example, washing with the washing solution may be carried out by sequentially carrying out the following steps: step (i) adding the washing solution (to the treated product or the remaining precipitate obtained in (iii) below) and stirring; step (ii) centrifuging the stirred product; and step (iii) discarding the supernatant after centrifugation. Steps (i) to (iii) may be repeated two or more times, for example, 15 or less times.

[0048] Step (d): In step (d), an intercalation treatment is performed using a metal compound containing a metal cation to intercalate the metal cation into the etching and cleaning treatment product, thereby obtaining an intercalation treatment product. As a result, the metal cation is intercalated into two adjacent M m X n An intercalated product is obtained in which the intercalation is carried out between the layers. Such an intercalation process may be carried out in a dispersion medium.

[0049] The metal cation may be the same as the metal cation contained in the two-dimensional particle, including Li cations, and may also contain other metal cations, provided that the metal of the metal cation is different from the M atom, and the metal of the metal cation is different from the A atom contained in the precursor.

[0050] Examples of the metal compound include ionic compounds in which the metal cation and anion are bonded. Examples include iodides, phosphates, sulfides including sulfates, nitrates, acetates, and carboxylates of the metal cations. The metal cation is preferably a lithium ion, and the metal compound is preferably a metal compound containing a lithium ion, more preferably an ionic compound of a lithium ion, and even more preferably one or more of an iodide, a phosphate, and a sulfide salt of a lithium ion. If a lithium ion is used as the metal ion, it is thought that the water hydrated with the lithium ion has the most negative dielectric constant, making it easier to form a monolayer.

[0051] The specific method for the intercalation treatment is not particularly limited, and for example, the etched and washed product may be mixed with a metal compound and stirred or allowed to stand. For example, stirring at room temperature may be used. Examples of the stirring method include a method using a stirring bar such as a stirrer, a method using a stirring blade, a method using a mixer, and a method using a centrifugal device. The stirring time can be set depending on the production scale of the single-layer / few-layer MXene particles, and can be set, for example, between 12 and 24 hours.

[0052] The intercalation treatment may be carried out in the presence of a dispersion medium, such as water, or an organic medium such as N-methylpyrrolidone, N-methylformamide, N,N-dimethylformamide, methanol, ethanol, dimethyl sulfoxide, ethylene glycol, or acetic acid.

[0053] The order of mixing the dispersion medium, the etching-cleaned product, and the metal compound is not particularly limited, but in one embodiment, the dispersion medium and the etching-cleaned product may be mixed together, and then the metal compound may be mixed in. Typically, the etching liquid after the etching treatment may be used as the dispersion medium.

[0054] The intercalation treatment is typically carried out on the etching-cleaned product, but in another embodiment, it may be carried out on the precursor simultaneously with the etching treatment. Specifically, the etching and intercalation treatment include mixing the precursor, an etching solution, and a metal compound containing a metal cation to remove at least a part of the A atoms from the precursor, and intercalating the metal cation into the precursor from which the A atoms have been removed, thereby obtaining an intercalation-treated product. As a result, at least a part of the A atoms are removed from the precursor (MAX), and the M in the precursor is removed. m X n The layer remains, and multiple adjacent M m X n An intercalation product is obtained in which metal cations are intercalated between the layers.

[0055] The etching solution and metal compound used in the etching and intercalation treatment may be the same as the etching solution and metal compound used in step (b), respectively.

[0056] Step (e): In step (e), the intercalation-treated product is stirred to perform a delamination process for delaminating the intercalation-treated product, thereby obtaining a delamination-treated product. By this stirring, shear stress is applied to the intercalation-treated product, and two adjacent M m Xn At least a portion of the space between the layers can be peeled off, and the MXene particles can be divided into a single layer or a few layers.

[0057] The conditions for the delamination treatment are not particularly limited and can be performed by known methods. For example, a method of applying shear stress to the intercalation-treated product includes dispersing the intercalation-treated product in a dispersion medium and stirring the mixture. Examples of stirring methods include stirring using a mechanical shaker, vortex mixer, homogenizer, ultrasonic treatment, hand shake, automatic shaker, etc. The degree of stirring, such as the stirring speed and stirring time, can be adjusted depending on the amount and concentration of the product to be treated. For example, the above-mentioned intercalation-treated slurry can be centrifuged to discard the supernatant, and then pure water can be added to the remaining precipitate, followed by stirring using, for example, a hand shake or automatic shaker to separate the layers. Removal of unexfoliated material can be achieved by centrifuging the mixture, discarding the supernatant, and then washing the remaining precipitate with water. For example, (i) pure water can be added to the remaining precipitate after discarding the supernatant, followed by stirring, (ii) centrifuging, and (iii) recovering the supernatant. The steps (i) to (iii) can be repeated at least once, preferably at least twice, but not more than 10 times to obtain a supernatant containing single-layer and few-layer MXene particles as a delamination-treated product. Alternatively, the supernatant can be centrifuged and discarded to obtain a clay containing single-layer and few-layer MXene particles as a delamination-treated product.

[0058] The delamination-treated product may be further washed. By such washing, at least some of the impurities can be removed. Hereinafter, the treated product obtained by washing the delamination-treated product is also referred to as a delamination-washed product, and the delamination-washed product is included in the technical scope of the delamination-treated product.

[0059] In one embodiment, the cleaning can be performed using a cleaning solution, typically by mixing the delamination-treated product with the cleaning solution. In another embodiment, the cleaning can be performed by acid-treating the delamination-treated product and then mixing the acid-treated product with the cleaning solution. Examples of such acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, hydroiodic acid, hydrobromic acid, and hydrofluoric acid; and organic acids such as acetic acid, citric acid, oxalic acid, benzoic acid, and sorbic acid. The acid concentration in the acid solution can be adjusted appropriately depending on the delamination-treated product. The cleaning with the cleaning solution can be performed sequentially by: step (i) adding the cleaning solution to the treated product or the remaining precipitate obtained in (iii) below and stirring; step (ii) centrifuging the stirred product; and step (iii) discarding the supernatant after centrifugation. Steps (i) to (iii) can be repeated two or more times, for example, up to 15 times. The stirring can be carried out using a handshake, an automatic shaker, a shear mixer, a pot mill, or the like. The acid treatment may be carried out one or more times, and if necessary, the operation of mixing with a fresh acid solution (an acid solution not used in the acid treatment) and stirring may be carried out two or more times, for example, up to 10 times. The washing liquid can be the same as the washing liquid in step (c). For example, water may be used as the washing liquid, and pure water is preferred. The mixing can be carried out by the same method as the mixing method in step (c), for example, by stirring, centrifugation, or the like. Stirring methods include stirring methods using a handshake, an automatic shaker, a shear mixer, a pot mill, or the like.

[0060] The intermediates and final products in the above-described production methods, for example, the intercalation-treated product and the delamination-treated product, may be dried by suction filtration, heat drying, freeze drying, vacuum drying, or the like.

[0061] The proportion of two-dimensional particles in the film of the present disclosure may be preferably 20% by volume or more and 100% by volume or less, more preferably 50% by volume or more and 100% by volume or less, even more preferably 70% by volume or more and 100% by volume or less, even more preferably 90% by volume or more and 100% by volume or less, and even more preferably 95% by volume or more and 100% by volume or less.

[0062] The adsorbent of the present disclosure may further contain, in addition to the two-dimensional particles, one or more materials selected from ceramics, metals, and resins. For example, when the adsorbent of this embodiment contains a material such as ceramics, metals, or resins, it may be easier to stably exhibit adsorption performance.

[0063] Examples of the ceramics include metal oxides such as silica, alumina, zirconia, titania, magnesia, cerium oxide, zinc oxide, barium titanate, hexaferrite, and mullite, and non-oxide ceramics such as silicon nitride, titanium nitride, aluminum nitride, silicon carbide, titanium carbide, tungsten carbide, boron carbide, and titanium boride.

[0064] Examples of the metal include metals of Groups 2 to 13, such as iron, titanium, magnesium, and aluminum; and alloys based on the metals of Groups 2 to 13.

[0065] The resin may be either a natural resin or a synthetic resin, and may be a hydrophilic resin or a hydrophobic resin. Such hydrophilic resins may include those obtained by blending a hydrophilic auxiliary such as a surfactant with a hydrophobic resin to exhibit hydrophilicity, and those obtained by modifying a part of a hydrophobic resin with a hydrophilic group.

[0066] Examples of the hydrophilic resin include resins having a polar group (for example, a hydroxyl group, a substituted or unsubstituted amino group, a carboxyl group, a sulfonic acid group, a carbonyl group, an ester bond, an amide bond, etc.), and specific examples include cellulose-based resins such as cellulose, cellulose acetate, and regenerated cellulose; polysulfone-based resins such as polysulfone and polyethersulfone; hydrophilic polyurethane; polyvinyl alcohol and copolymers thereof; sodium alginate; acrylic resins; substituted or unsubstituted polyacrylamide; acrylonitrile; polyaniline sulfonic acid; and polyamide resins such as nylon.

[0067] In one embodiment, the hydrophilic resin is preferably a resin having, as the polar group, a group capable of modifying the layer or forming a hydrogen bond with the terminal T. Examples of such groups include hydroxyl groups, carboxyl groups, sulfonic acid groups, carbonyl groups, and amide bonds. Examples of resins having these groups include water-soluble polyurethane, polyvinyl alcohol, sodium alginate, acrylic acid-based water-soluble polymers, polyacrylamide, polyaniline sulfonic acid, and nylon. Of these, water-soluble polyurethane, polyvinyl alcohol, and sodium alginate are preferred, and water-soluble polyurethane is more preferred.

[0068] In another aspect, the hydrophilic resin is preferably an acrylic resin, polyacrylonitrile, cellulose resin, polysulfone resin, polyvinyl alcohol, or a copolymer thereof, more preferably polymethyl methacrylate, polyacrylonitrile, cellulose, cellulose acetate, polysulfone, polyvinyl alcohol, or a copolymer of polyvinyl alcohol and polyethylene, even more preferably polysulfone, polymethyl methacrylate, or cellulose acetate, and even more preferably polysulfone or polymethyl methacrylate. These resins can be used in dialysis, hemofiltration, and the like, and may be suitable when the adsorbent of the present disclosure is applied to a dialysis device.

[0069] Examples of the hydrophobic resin include resins that do not contain the polar groups.

[0070] The adsorbent of the present disclosure can be manufactured using the two-dimensional particles. The two-dimensional particles may be used as the adsorbent of the present disclosure as they are, or the two-dimensional particles may be mixed with one or more materials selected from ceramics, metals, and resins, as needed, and molded into a predetermined shape to form the adsorbent.

[0071] In one embodiment, when the adsorbent contains a resin, the adsorbent can be produced by mixing the two-dimensional particles with the resin to form a mixture and molding the mixture.

[0072] The two-dimensional particles and the resin may be mixed without a solvent or in the presence of a dispersion medium, which is typically water, and may optionally contain a relatively small amount of other liquid substance in addition to water (for example, 30% by mass or less, preferably 20% by mass or less, based on the total).

[0073] The two-dimensional particles and resin can be stirred using a dispersing device such as a homogenizer, a propeller stirrer, a thin film rotary stirrer, a planetary mixer, a mechanical shaker, or a vortex mixer.

[0074] The molding method is not particularly limited, and for example, a mixture of the two-dimensional particles and resin may be molded into a predetermined shape as is, or the two-dimensional particles, resin, and dispersion medium may be mixed to obtain a mixture, which may be applied to a substrate (e.g., a substrate) to obtain a precursor film containing the dispersion medium, and the precursor film may be dried to remove at least a portion of the dispersion medium contained in the precursor film to form a film. Examples of the coating method include spray coating using a nozzle such as a one-fluid nozzle, a two-fluid nozzle, or an airbrush, slit coating using a table coater, comma coater, or bar coater, screen printing, metal mask printing, and other coating methods such as spin coating, immersion, and dripping.

[0075] The coating and drying steps may be repeated multiple times as necessary until a film of the desired thickness is obtained. The drying may be carried out at a temperature of 400° C. or less using, for example, an atmospheric pressure oven or a vacuum oven.

[0076] In another aspect, when the adsorbent comprises a ceramic or metal, the adsorbent can be produced by mixing the two-dimensional particles with, for example, particulate ceramic or metal, and heating at a low temperature that maintains the composition of the two-dimensional particles.

[0077] The adsorbent is used to adsorb disease-causing substances, for example, to remove or reduce disease-causing substances in blood by adsorption. The ability of the adsorbent to adsorb disease-causing substances can be confirmed, for example, by adsorption tests using human plasma.

[0078] The disease-causing substance preferably includes a protein. Examples of such proteins include uremic proteins (specifically, medium-molecular-weight uremic substances) such as parathyroid hormone, β2-microglobulin, and tumor necrosis factor (TNF)-α; cytokines (in one embodiment, inflammatory cytokines such as interleukins, interferons, chemokines, hematopoietic factors, growth factors, and tumor necrosis factors); and other proteins such as albumin and M protein. The uremic proteins (specifically, medium-molecular-weight uremic substances) are uremic substances, and adsorption of these is expected to have a preventive effect against uremia. The inflammatory cytokines can cause various inflammatory symptoms in the body, and adsorption of these is expected to have a preventive effect against inflammation. In this disclosure, "uremic" means that the concentration in the blood increases with a decline in kidney function, and can cause various symptoms associated with kidney diseases such as acute kidney injury (including acute renal failure) and chronic kidney disease (including chronic renal failure and end-stage renal failure), particularly various symptoms associated with kidney injury.

[0079] Furthermore, by adsorbing inflammatory substances as disease-causing substances, it is expected to have a preventive effect on various symptoms associated with inflammatory diseases, such as vascular dementia, inflammatory bowel disease, hepatitis, and myocarditis.

[0080] The disease-causing substance preferably contains an electrolyte (ionic substance). That is, the adsorbent can also be used to adsorb electrolytes. Such electrolytes include cations and anions. Such cations include cations that can be excreted in the kidney, specifically, Na + , K. + , Mg 2+ , Ca 2+ In the present disclosure, anions include anions that can be excreted in the kidney, specifically anions including P (e.g., PO 4 3- ) are listed.

[0081] When renal function declines, the blood concentrations of the above electrolytes (particularly those that can be excreted by the kidneys) may increase, which can lead to electrolyte metabolism disorders such as hypernatremia, hyperkalemia, hypermagnesemia, and hyperphosphatemia. By adsorbing these electrolytes using the above amount of adsorbent, it is expected that the effect of preventing electrolyte metabolism disorders will be achieved.

[0082] The disease-causing substances preferably further include protein-bound uremic substances such as creatinine, homocysteine, indoxyl sulfate, and p-cresyl sulfate; carcinogenic substances, etc. In other words, the adsorbent can also be used to adsorb protein-bound uremic substances and carcinogenic substances. Therefore, by using an adsorbent containing the two-dimensional particles as a separation membrane in a dialysis device, it is expected to be effective in treating or preventing the various diseases mentioned above.

[0083] The adsorbent of the present disclosure is expected to be able to adsorb the above-mentioned adsorbates and thereby prevent or treat various symptoms associated with kidney diseases such as acute kidney injury (including acute renal failure) and chronic kidney disease (including chronic renal failure and end-stage renal failure), as well as various symptoms associated with inflammatory diseases, particularly various symptoms associated with kidney injury and / or inflammatory diseases. Specifically, the adsorbent is expected to prevent or treat uremia; electrolyte metabolism disorders such as hypernatremia, hyperkalemia, hypermagnesemia, and hyperphosphatemia; autoimmune diseases; infectious diseases; inflammatory diseases; endocrine and metabolic diseases; cardiovascular diseases; blood diseases; digestive diseases; neurological diseases; malignant tumors; drug addiction; and inflammatory diseases such as vascular dementia, inflammatory bowel disease, hepatitis, and myocarditis.

[0084] An adsorption method including adsorbing the disease-causing substance using the adsorbent is also encompassed within the technical scope of the present disclosure. Such an adsorption method preferably includes adsorbing a protein as the disease-causing substance using the adsorbent. The adsorption method may further include adsorbing an electrolyte as the disease-causing substance. That is, the adsorption method may include adsorbing the protein and electrolyte as the disease-causing substances using the adsorbent. The adsorption method may further include adsorbing another adsorbate using the adsorbent. In one aspect, the adsorption of such a disease-causing substance can be carried out by contacting the adsorbent with a liquid containing an adsorbate such as a protein or electrolyte as the disease-causing substance. The liquid containing the adsorbate may contain substances other than proteins and electrolytes as the disease-causing substance. Specific examples of the liquid containing the adsorbate include blood, dialysis fluid, etc.

[0085] (Embodiment 2: Adsorption Sheet) The adsorption sheet in this embodiment contains the adsorbent described above. By including the adsorbent, such an adsorption sheet can adsorb a variety of adsorbates, particularly disease-causing substances, and can also physically fix the adsorbent, thereby enabling the adsorption performance to be stably exhibited.

[0086] The adsorption sheet in this embodiment may be made of the adsorbent material described above, or may further contain, in addition to the adsorbent material, one or more materials selected from the ceramics, metals, and resins described above. As such ceramics, metals, and resins, the same materials as those that can be contained in the adsorbent material can be used.

[0087] When the adsorption sheet in this embodiment further contains one or more materials selected from the ceramics, metals, and resins, the adsorption sheet may comprise a member in which the adsorbent and the material are uniformly mixed, or may comprise a member containing the adsorbent and a member containing the material.

[0088] In one aspect, the adsorbent sheet of the present embodiment may include a substrate containing one selected from the group consisting of ceramics, metals, and resins, and a membrane containing the adsorbent and disposed on the substrate. The membrane containing the adsorbent covers at least a portion of the surface of the substrate, or may cover the entire surface of the substrate.

[0089] The adsorbent sheet can be produced by forming a film containing an adsorbent on the surface of the substrate. The method for producing the adsorbent-containing film is not particularly limited, and may include, for example, mixing the two-dimensional particles with a dispersion medium and, if necessary, two-dimensional particles to obtain a mixture, applying the mixture to the substrate to obtain a precursor film containing the dispersion medium, and drying the precursor film to remove at least a portion of the dispersion medium contained in the precursor film to form a film. The mixture can be applied to the substrate by, for example, immersion, brushing, roller coating, roll coating, air spraying, airless coating, curtain flow coating, roller curtain coating, die coating, electrostatic coating, or other commonly used coating methods. The thickness of the adsorbent sheet and the thickness of the substrate can be appropriately set depending on the application.

[0090] (Embodiment 3: Separation membrane) The separation membrane in this embodiment contains the adsorbent. By containing the adsorbent, such a separation membrane can adsorb a variety of adsorbates, particularly disease-causing substances, and because the adsorbent can be physically fixed, it can stably exhibit adsorption performance. The separation membrane in this embodiment is particularly suitable as a separation membrane for artificial dialysis used in the above-mentioned hemodialysis, etc.

[0091] The separation membrane may be made of the adsorbent, or may further contain, in addition to the adsorbent, one or more materials selected from the ceramics, metals, and resins. In one embodiment, the separation membrane may include a substrate, a substrate containing one material selected from the ceramics, metals, and resins, and a membrane containing the adsorbent and disposed on the substrate. The membrane containing the adsorbent may cover at least a portion of the surface of the substrate, or may cover the entire surface of the substrate. The shape of the substrate is not particularly limited and may be a film, sheet, plate, porous, hollow fiber, bead, or the like.

[0092] The ceramics, metals, and resins may be the same as the ceramics, metals, and resins that can be contained in the adsorbent. Among these, cellulose-based and synthetic polymer-based materials used in hemodialysis and the like are preferred. Specifically, polymethyl methacrylate, polyacrylonitrile, cellulose, cellulose acetate, polysulfone, polyvinyl alcohol, and vinyl alcohol copolymers such as copolymers of polyvinyl alcohol and ethylene are preferred. Polysulfone, polymethyl methacrylate, and cellulose acetate are more preferred, and polysulfone and polymethyl methacrylate are even more preferred. The form of the separation membrane for artificial dialysis is not particularly limited, and examples thereof include porous, hollow fiber, and flat membrane laminate types.

[0093] (Embodiment 4: Dialysis Device) The dialysis device in this embodiment includes the above-mentioned adsorbent. By including the above-mentioned adsorbent, such an dialysis device can adsorb a variety of adsorbates, particularly disease-causing substances, and can be used to adsorb and remove various waste products in hemodialysis, hemofiltration, hemodiafiltration, peritoneal dialysis, etc. In other words, the adsorbent of this embodiment can be used in dialysis devices for performing the above-mentioned hemodialysis, hemofiltration, hemodiafiltration, peritoneal dialysis, etc.

[0094] The above-mentioned dialysis machines are classified into, for example, hemodialysis machines and peritoneal dialysis machines, and hemodialysis machines are divided into one-pass (single-pass) and circulating types. Furthermore, circulating types include REDY systems (recirculating dialysate systems) and other systems. The above-mentioned dialysis machines are also classified according to the method of removing urea without contact with the blood by crossflow of the patient's blood and the dialysate, and the method of directly filtering the blood. Furthermore, the one-pass type is the mainstream for peritoneal dialysis machines. The adsorbent of this embodiment can be used for both hemodialysis and peritoneal dialysis, and can be used as an adsorption membrane, a separation membrane, an adsorbent cartridge, etc. in hemodialysis machines, peritoneal dialysis machines, and other dialysis machines. For example, when used in a REDY system (recirculating dialysate system), the adsorbent of this embodiment can be used in the adsorbent cartridge.

[0095] FIG. 2 schematically illustrates a one-pass hemodialysis device as an example of an artificial dialysis device using the adsorbent according to the present disclosure. In the hemodialysis device 40 of FIG. 2, untreated blood introduced through a blood inlet 41 is pumped to a blood purification device 44 by a blood pump 43. Meanwhile, dialysate is pumped from a fresh dialysate tank 48 to the blood purification device 44 by a dialysate pump 50. In the blood purification device 44, blood in a blood passage area 46 of the blood purification device is subjected to hemodialysis, hemodiafiltration, or hemofiltration by a separation membrane 45, and substances to be removed pass through the separation membrane 45 and move to a dialysate passage area 47 of the blood purification device. The purified blood is sent to a blood outlet 42. Meanwhile, the dialysate in the dialysate passage area 47 containing the substances to be removed is pumped to a used dialysate tank 49. Although not shown in FIG. 2, a device including a path for replenishing drugs, proteins, etc., to the blood as needed during the pumping of the blood before and / or after treatment may also be provided. In addition, sensors for measuring the blood flow rate, the dialysate flow rate, and, if necessary, the protein concentration in the blood may be provided, and on-off valves for opening and closing the blood and / or dialysate flow paths may be provided in the blood and / or dialysate flow paths as necessary.

[0096] Figure 3 shows a schematic diagram of a one-pass hemodialysis machine as another example of an artificial dialysis machine using the adsorbent according to the present disclosure. The hemodialysis machine 40A in Figure 2 differs from the hemodialysis machine 40 in Figure 2 in that a separation membrane 45A is disposed between a blood pump 43A and a blood purification machine 44A, and that a semipermeable membrane 51A is disposed in the blood purification machine as a membrane for separating blood from dialysate. Other configurations are the same as those of the hemodialysis machine 40 in Figure 2, and the same reference numerals are used, and description thereof will be omitted.

[0097] In the hemodialysis device 40A of FIG. 3, the blood is brought into contact with the separation membrane 45A before passing through the blood purification device 44A, thereby allowing adsorbates such as disease-causing substances to be adsorbed, thereby improving dialysis efficiency.

[0098] Separation membrane 45A may be clad with a resin or the like and arranged in the form of a column, and filters may be placed on the blood inlet and outlet sides of the column so that blood is distributed throughout separation membrane 45A.

[0099] In the hemodialysis machine 40A of FIG. 3, the membrane that separates the blood from the dialysate is the semipermeable membrane 51A, but the separation membrane of the present disclosure may be used instead of the semipermeable membrane 51A.

[0100] The present invention will be explained in more detail with reference to the following examples, but the present invention is not limited to these examples.

[0101] Example 1 [Preparation of MXene] In Examples 1 and 2, two-dimensional particles were prepared by sequentially carrying out the following steps, as detailed below: (1) preparation of a precursor (MAX), (2) etching of the precursor, and (3) washing and drying.

[0102] (1) Preparation of Precursor (MAX) TiC powder, Ti powder, and Al powder (all manufactured by Kojundo Chemical Laboratory Co., Ltd.) were mixed in a molar ratio of 2:1:1 in a ball mill containing zirconia balls for 24 hours. The resulting mixed powder was sintered at 1,350°C for 2 hours in an Ar atmosphere. The resulting sintered body (block) was then pulverized with an end mill to a maximum size of 40 μm or less. This resulted in the preparation of TiC precursor (MAX). 3 AlC 2 particles were obtained.

[0103] (2) Etching of the precursor Ti prepared by the above method 3 AlC 2 Using particles (powder), etching was performed under the following etching conditions to remove Ti 3 AlC 2 A solid-liquid mixture (slurry) containing solid components derived from the powder was obtained. (Etching conditions) Precursor: Ti 3 AlC 2 (Sieved through a 45 μm mesh) Etching solution composition: 50% by mass HF 6 mL, H 2O 18 mL HCl (12 M) 36 mL Precursor input amount: 3.0 g Etching container: 100 mL Eye Boy Etching temperature: 35°C Etching time: 24 h Stirrer rotation speed: 400 rpm

[0104] (3) Washing and drying The slurry was divided into two parts and placed in two 50 mL centrifuge tubes, respectively. After centrifuging at 3,500 G using a centrifuge, the supernatant was discarded. 40 mL of pure water was added to each centrifuge tube, and the tubes were centrifuged again at 3,500 G to separate and remove the supernatant. This procedure was repeated 11 times. After the final centrifugation, the supernatant was discarded, and Ti 3 C 2 T s - A water medium clay was obtained. The obtained clay was freeze-dried to dry powder, and a dry powder of two-dimensional particles was obtained.

[0105] In Example 2, (1) a precursor (MAX) was prepared in the same manner as in Example 1, and then the following step (2) was carried out. (3) Cleaning and drying were carried out in the same manner as in Example 1 to produce two-dimensional particles. (1) Precursor preparation: same as in Example 1. (2) Precursor etching: Precursor: Ti 3 AlC 2 (Sieved through a 45 μm mesh) Etching solution composition: 50% by mass HF 5 mL, 2 O 45 mL Precursor input amount: 3.0 g Etching container: 100 mL Eye Boy Etching temperature: 35°C Etching time: 24 hours Stirrer rotation speed: 400 rpm (3) Cleaning: Same as in Example 1

[0106] In Example 3, (1) a precursor (MAX) was prepared in the same manner as in Example 1, and then the following step (2) was carried out, and (3) washing and drying were carried out in the same manner as in Example 1 to produce two-dimensional particles. (1) Precursor preparation: same as in Example 1 (2) Precursor etching Precursor: Ti 3 AlC 2 (Passed through a 45 μm sieve) Etching solution composition: 6 mL of 49% by mass HF aqueous solution, 2O 9mL 85% by mass H 3 P.O. 4 Aqueous solution: 45 mL Amount of precursor added: 3.0 g Etching container: 100 mL Eye Boy Etching temperature: 35°C Etching time: 24 hours Stirrer rotation speed: 400 rpm (3) Cleaning: Same as in Example 1

[0107] In Example 4, (1) a precursor (MAX) was prepared in the same manner as in Example 1, and then the following step (2) was carried out, and (3) washing and drying were carried out in the same manner as in Example 1 to produce two-dimensional particles. (1) Precursor preparation: same as in Example 1 (2) Precursor etching Precursor: Ti 3 AlC 2 (Passed through a 45 μm mesh sieve) Etching solution composition: LiF 4.8 g, HCl (9 M) 60 mL Amount of precursor added: 3.0 g Etching container: 100 mL Eye Boy Etching temperature: 35° C. Etching time: 24 hours Stirrer rotation speed: 400 rpm (3) Cleaning: Same as in Example 1

[0108] Example 5 In Example 5, two-dimensional particles were fabricated by sequentially carrying out the following steps, as detailed below: (1) preparation of a precursor (MAX), (2) etching of the precursor, and (3) washing and drying.

[0109] (1) Preparation of Precursor (MAX) 73 g of Ti powder, 47.2 g of TiN powder, 20.6 g of Al powder, and 9.2 g of C powder (all manufactured by Kojundo Chemical Laboratory Co., Ltd.) were placed in a ball mill containing zirconia balls and mixed for 24 hours. The resulting mixed powder was fired at 1,400 °C for 2 hours in an Ar atmosphere. The fired body (block) thus obtained was pulverized with an end mill to a maximum dimension of 40 μm or less. As a result, TiN powder was prepared as a precursor (MAX). 3 AlCN particles were obtained.

[0110] (2) Etching of the precursor Ti prepared by the above method 3 Etching was performed using AlCN particles (powder) under the following etching conditions to remove Ti. 3A solid-liquid mixture (slurry) containing solid components derived from the AlCN powder was obtained. (Etching conditions) Precursor: Ti 3 AlCN (passed through a 45 μm sieve) Etching solution composition: 48 mass% HF 6 mL 38.8 mass% HCl 36 mL H 2 O 18 mL Precursor input amount: 3.0 g Etching container: 100 mL Eye Boy Etching temperature: 25°C Etching time: 24 h Stirrer rotation speed: 400 rpm

[0111] (3) Washing and drying The slurry was divided into two parts and placed in two 50 mL centrifuge tubes, respectively. After centrifuging at 3,500 G using a centrifuge, the supernatant was discarded. 40 mL of pure water was added to each centrifuge tube, and the tubes were centrifuged again at 3,500 G to separate and remove the supernatant. This procedure was repeated 11 times. After the final centrifugation, the supernatant was discarded, and Ti 3 CNT s - A water medium clay was obtained. The obtained clay was freeze-dried to dry powder, and a dry powder of two-dimensional particles was obtained.

[0112] Example 6 In Example 6, two-dimensional particles were fabricated by sequentially carrying out the following steps, as detailed below: (1) preparation of a precursor (MAX), (2) etching of the precursor, and (3) washing and drying.

[0113] (1) Preparation of Precursor (MAX) 21.5 g of V powder, 6.3 g of Al powder, and 2.3 g of C powder (all manufactured by Kojundo Chemical Laboratory Co., Ltd.) were placed in a ball mill containing zirconia balls and mixed for 24 hours. The resulting mixed powder was fired at 1,550 °C for 2 hours in an Ar atmosphere. The fired body (block) obtained was crushed in a jaw crusher to a maximum size of 45 μm or less. As a result, V was prepared as a precursor (MAX). 2 AlC particles were obtained.

[0114] (2) Etching of precursor V prepared by the above method 2 Etching was performed using AlC particles (powder) under the following etching conditions. 2A solid-liquid mixture (slurry) containing solid components derived from the AlC powder was obtained. (Etching conditions) Precursor: V 2 AlC (passed through a 45 μm sieve) Etching solution composition: 48 mass% HF 6 mL 38.8 mass% HCl 24 mL Amount of precursor added: 3.0 g Etching container: 100 mL Eye Boy Etching temperature: 50°C Etching time: 48 hours Stirrer rotation speed: 400 rpm

[0115] (3) Washing and drying The slurry was divided into two parts and placed in two 50 mL centrifuge tubes, respectively. After centrifuging at 3,500 G using a centrifuge, the supernatant was discarded. 40 mL of pure water was added to each centrifuge tube, and the tubes were centrifuged again at 3,500 G to separate and remove the supernatant. This procedure was repeated 11 times. After the final centrifugation, the supernatant was discarded, and the V 2 CT s - A water medium clay was obtained. The obtained clay was freeze-dried to dry powder, and a dry powder of two-dimensional particles was obtained.

[0116] Example 7 In Example 7, two-dimensional particles were fabricated by sequentially carrying out the following steps, as detailed below: (1) preparation of a precursor (MAX), (2) etching of the precursor, and (3) washing and drying.

[0117] (1) Preparation of Precursor (MAX) 105.4 g of Ti powder, 32.7 g of Al powder, and 11.9 g of C powder (all manufactured by Kojundo Chemical Laboratory Co., Ltd.) were placed in a ball mill containing zirconia balls and mixed for 24 hours. The resulting mixed powder was sintered at 1,550 °C for 2 hours in an Ar atmosphere. The resulting sintered body (block) was pulverized with an end mill to a maximum dimension of 40 μm or less. This resulted in the preparation of Ti as a precursor (MAX). 2 AlC particles were obtained.

[0118] (2) Etching of the precursor Ti prepared by the above method 2 Etching was performed using AlC particles (powder) under the following etching conditions to remove Ti. 2 A solid-liquid mixture (slurry) containing solid components derived from the AlC powder was obtained. (Etching conditions) Precursor: Ti 2AlC (passed through a 45 μm mesh sieve) Etching solution composition: 48 mass% HF 2 mL 38.8 mass% HCl 12 mL H 2 Precursor input amount: 1.0 g Etching container: 100 mL Eye Boy Etching temperature: 35°C Etching time: 24 h Stirrer rotation speed: 400 rpm

[0119] (3) Washing and drying The slurry was divided into two parts and placed in two 50 mL centrifuge tubes, respectively. After centrifuging at 3,500 G using a centrifuge, the supernatant was discarded. 40 mL of pure water was added to each centrifuge tube, and the tubes were centrifuged again at 3,500 G to separate and remove the supernatant. This procedure was repeated 11 times. After the final centrifugation, the supernatant was discarded, and Ti 2 CT s - A water medium clay was obtained. The obtained clay was freeze-dried to dry powder, and a dry powder of two-dimensional particles was obtained.

[0120] Example 8 In Example 8, two-dimensional particles were fabricated by sequentially carrying out the following steps, as detailed below: (1) preparation of a precursor (MAX), (2) etching of the precursor, and (3) washing and drying.

[0121] (1) Preparation of Precursor (MAX) TiC powder, Ti powder, and Al powder (all manufactured by Kojundo Chemical Laboratory Co., Ltd.) were mixed in a molar ratio of 2:1:1 in a ball mill containing zirconia balls for 24 hours. The resulting mixed powder was sintered at 1350°C for 2 hours in an Ar atmosphere. The resulting sintered body (block) was then pulverized with an end mill to a maximum size of 40 μm or less. As a result, TiC powder was obtained as MAX particles. 3 AlC 2 particles were obtained.

[0122] (2) Etching of the precursor Ti prepared by the above method 3 AlC 2 Using particles (powder), etching was performed under the following etching conditions to remove Ti 3 AlC 2 A solid-liquid mixture (slurry) containing solid components derived from the powder was obtained. (Etching conditions) Precursor: Ti 3 AlC2 (Sieved through a 45 μm mesh) Etching solution composition: 48% HF 6 mL H 2 O 54 mL Precursor input amount: 3.0 g Etching container: 100 mL Eye Boy Etching temperature: 50°C Etching time: 24 h Stirrer rotation speed: 400 rpm

[0123] (3) Washing and drying The slurry was divided into two parts and placed in two 50 mL centrifuge tubes, respectively. After centrifuging at 3500 G using a centrifuge, the supernatant was discarded. 40 mL of pure water was added to the remaining precipitate in each centrifuge tube, and the tubes were centrifuged again at 3500 G to separate and remove the supernatant. This procedure was repeated 11 times. After the final centrifugation, the supernatant was discarded, and Ti 3 C 2 T x - A water-containing clay was obtained. The obtained clay was freeze-dried to dry powder, and a dry powder of two-dimensional particles was obtained.

[0124] Example 9 In Example 9, two-dimensional particles were fabricated by sequentially carrying out the following steps, as detailed below: (1) preparation of a precursor (MAX), (2) etching of the precursor, and (3) washing and drying.

[0125] (1) Preparation of Precursor (MAX) TiC powder, Ti powder, and Al powder (all manufactured by Kojundo Chemical Laboratory Co., Ltd.) were mixed in a molar ratio of 2:1:1 in a ball mill containing zirconia balls for 24 hours. The resulting mixed powder was sintered at 1350°C for 2 hours in an Ar atmosphere. The resulting sintered body (block) was then pulverized with an end mill to a maximum size of 40 μm or less. As a result, TiC powder was obtained as MAX particles. 3 AlC 2 particles were obtained.

[0126] (2) Etching of the precursor Ti prepared by the above method 3 AlC 2 Using particles (powder), etching was performed under the following etching conditions to remove Ti 3 AlC 2 A solid-liquid mixture (slurry) containing solid components derived from the powder was obtained. (Etching conditions) Precursor: Ti 3 AlC2 (Passed through a 45 μm sieve) Etching solution composition: 48 mass% HF 6 mL 38.8 mass% HCl 38 mL H 2 O 16 mL Precursor input amount: 3.0 g Etching container: 100 mL Eye Boy Etching temperature: 50°C Etching time: 24 h Stirrer rotation speed: 400 rpm

[0127] (3) Washing and drying The slurry was divided into two parts and placed in two 50 mL centrifuge tubes, respectively. After centrifuging at 3500 G using a centrifuge, the supernatant was discarded. 40 mL of pure water was added to the remaining precipitate in each centrifuge tube, and the tubes were centrifuged again at 3500 G to separate and remove the supernatant. This procedure was repeated 11 times. After the final centrifugation, the supernatant was discarded, and Ti 3 C 2 T x - A water-containing clay was obtained. The obtained clay was freeze-dried to dry powder, and a dry powder of two-dimensional particles was obtained.

[0128] Example 10 In Example 10, two-dimensional particles were fabricated by sequentially carrying out the following steps, as detailed below: (1) preparation of a precursor (MAX), (2) etching of the precursor, (3) washing, (4) Li intercalation, (5) delamination, and (6) modification with amino groups and drying.

[0129] (1) Preparation of Precursor (MAX) TiC powder, Ti powder, and Al powder (all manufactured by Kojundo Chemical Laboratory Co., Ltd.) were mixed in a molar ratio of 2:1:1 in a ball mill containing zirconia balls for 24 hours. The resulting mixed powder was sintered at 1350°C for 2 hours in an Ar atmosphere. The resulting sintered body (block) was then pulverized with an end mill to a maximum size of 40 μm or less. As a result, TiC powder was obtained as MAX particles. 3 AlC 2 particles were obtained.

[0130] (2) Etching of the precursor Ti prepared by the above method 3 AlC 2 Using particles (powder), etching was performed under the following etching conditions to remove Ti 3 AlC2 A solid-liquid mixture (slurry) containing solid components derived from the powder was obtained. (Etching conditions) Precursor: Ti 3 AlC 2 (Passed through a 45 μm sieve) Etching solution composition: 48 mass% HF 2 mL 38.8 mass% HCl 38 mL H 2 O 16 mL Precursor input amount: 3.0 g Etching container: 100 mL Eye Boy Etching temperature: 50°C Etching time: 24 h Stirrer rotation speed: 400 rpm

[0131] (3) Washing and drying The slurry was divided into two parts and placed in two 50 mL centrifuge tubes, respectively. After centrifuging at 3500 G using a centrifuge, the supernatant was discarded. 40 mL of pure water was added to the remaining precipitate in each centrifuge tube, and the tubes were centrifuged again at 3500 G to separate and remove the supernatant. This procedure was repeated 11 times. After the final centrifugation, the supernatant was discarded, and Ti 3 C 2 T x -Water medium clay was obtained.

[0132] (4) Li intercalation Ti prepared by the above method 3 C 2 T x The clay was mixed with water as a medium, and LiCl was used as the Li-containing compound. The mixture was stirred at 20°C to 25°C for 12 hours under the following conditions to perform Li intercalation. (Li intercalation conditions) 3 C 2 T x - Water medium clay (MXene after washing): solid content 0.75 g LiCl: 0.75 g Intercalation container: 100 mL Eye Boy Temperature: 20 ° C or higher and 25 ° C or lower (room temperature) Time: 10 h Stirrer rotation speed: 800 rpm

[0133] (5) Delamination The above Ti 3 C 2 T x(i) 40 mL of pure water was added to the aqueous clay medium, followed by stirring for 15 minutes with a shaker. (ii) The mixture was centrifuged at 3,500 G, and (iii) the supernatant was collected as a single-layer MXene-containing solution. These steps (i) to (iii) were repeated four times to obtain a single-layer MXene-containing supernatant. This supernatant was then centrifuged at 4,300 G for two hours using a centrifuge, after which the supernatant was discarded, yielding a single-layer / scarce MXene-containing clay as a single-layer / scarce MXene-containing sample.

[0134] (6) Amino group modification and drying 20 mg of 6-aminohexyl phosphate hydrochloride and 5 mL of pure water were added to 0.34 g of single-layer and few-layer MXene-containing clay, and the mixture was stirred at room temperature for 2 hours at a stirrer speed of 800 rpm. The resulting slurry was centrifuged at 8,000 rpm for 8 minutes, and the supernatant was discarded. The same volume of pure water as the discarded supernatant was added, and the mixture was centrifuged at 8,000 rpm for 8 minutes. The procedure of discarding the supernatant, adding the same volume of pure water as the discarded supernatant, and centrifuging at 8,000 rpm for 8 minutes was repeated once. Next, the supernatant was discarded, and the same volume of ethanol as the discarded supernatant was added and dispersed, followed by air drying, to obtain amino group-modified Ti. 3 C 2 Particles (powder) were obtained.

[0135] Comparative Example 1 Spherical adsorptive carbon ("Kremezin Rapidly Disintegrating Tablets 500 mg", manufactured by Kureha Corporation) was powdered using a mortar and subjected to adsorption evaluation.

[0136] Comparative Example 2 An adsorption-type blood purifier ("Rixel", manufactured by Kaneka Corporation) was disassembled, and the removed adsorbent was subjected to adsorption evaluation.

[0137] Comparative Example 3 Medicinal charcoal (manufactured by Nichi-Iko Pharmaceutical Co., Ltd.) was subjected to adsorption evaluation.

[0138] Adsorption Evaluation Method: Human plasma collected from a healthy subject, the two-dimensional particles of the Examples, and the spherical adsorbent carbon, adsorptive blood purifier, or medicinal carbon of the Comparative Examples (hereinafter collectively referred to as "adsorbent") were weighed into a 50 mL centrifuge tube and shaken and stirred for 60 minutes using a thermostatic shaker (Tytec BR-33FL) set at 37°C. Several mL of the mixture was then sampled, and the adsorbent was separated using a syringe filter with a 0.45 μm pore size (Merck Millex Sterilization, diameter 33 mm, pore size 0.45 μm), followed by component analysis. In Examples 1 to 4 and Comparative Examples 1 to 3, the amount of human plasma was 10 mL, and the amount of adsorbent was 0.6 g; in Examples 5 to 8 and 10, the amount of human plasma was 4 mL, and the amount of adsorbent was 0.2 g; and in Example 9, the amount of human plasma was 4 mL, and the amount of adsorbent was 0.2 g.

[0139] In Examples 1 to 4 and Comparative Examples 1 to 3, component analysis was performed for Na, P, K, urea, creatinine, homocysteine, folic acid, parathyroid hormone, β2-microglobulin, interleukin-18, trypsin, TNF-α (tumor necrosis factor-α), α-amylase, and albumin. In Examples 5 to 10, component analysis was performed for albumin, chloride (Cl), serum urea nitrogen (BUN), α-amylase (AMY), lipase, Na, K, inorganic phosphorus (IP), and β2-microglobulin. Measurements of Na, K, and Cl were performed by the electrode method; measurements of P, inorganic phosphorus, α-amylase, lipase, and creatinine were performed by the enzymatic method; measurements of urea and serum urea nitrogen were performed by the urease-GLDH-UV method; measurements of homocysteine ​​were performed by the HPLC method; measurements of folic acid were performed by the CLIA method; measurements of parathyroid hormone were performed by the ECLIA method; measurements of β2-microglobulin were performed by the latex agglutination method; measurements of interleukin-18, trypsin, and TNF-α were performed by the EIA method; and measurements of albumin were performed by the colorimetric method (BGC method).

[0140] The same treatment was also carried out on a centrifuge tube containing only human plasma without any adsorbent, and this was used as a baseline for the component concentration. A1 , the concentration of component A at baseline is C A0 The adsorption and removal rate was calculated based on the following formula. When the adsorption and removal rate was less than 0 mass%, it was set to 0 mass%. Adsorption and removal rate (mass%) = (C A0 -C A1 ) / C A0 ×100

[0141] The results are shown in Tables 1 and 2.

[0142]

[0143]

[0144] The adsorbents of Examples 1 to 4 adsorb disease-causing substances such as parathyroid hormone, β2-microglobulin, tumor necrosis factor (TNF)-α and other middle molecular uremic substances; inflammatory cytokines such as interleukin-18; and proteins such as albumin. + , K. + It was confirmed that the two-dimensional particles exhibited the ability to adsorb electrolytes such as ATP, ATP-1, ATP-2, ATP-3, ATP-4, ATP-5, ATP-6, ATP-7, ATP-8, ATP-9, ATP-10, ATP-20, ATP-21, ATP-32, ATP-40, ATP-50, ATP-60, ATP-70, ATP-80, ATP-90, ATP-11, ATP-12, ATP-13, ATP-14, ATP-15, ATP-16, ATP-17, ATP-18, ATP-19, ATP-20, ATP-21, ATP-22, ATP-23, ATP-24, ATP-25, ATP-26, ATP-27, ATP-28, ATP-29, ATP-30, ATP-31, ATP-32, ATP-33, ATP-34, ATP-35, ATP-36, ATP-37, ATP-38, ATP-39, ATP-40, ATP-41, ATP-42, ATP-43, ATP-44, ATP-45, ATP-46, ATP-47, ATP-48, ATP-49, ATP-50, ATP-51, ATP-52, ATP-53, ATP-54, ATP-55, ATP-56, ATP-57, ATP-58, ATP-59, ATP-60, ATP-61, ATP-62, ATP-71, ATP-72, ATP-83, ATP-84, ATP-85, ATP-86, ATP-87, ATP-88, ATP-89, ATP-90, ATP-91, ATP-92

[0145] The adsorbents of Comparative Examples 1 to 3 did not contain the predetermined two-dimensional particles, and the results of the adsorption test confirmed that the adsorbates were limited. + , K. + It was not confirmed that the cellulose acylate adsorbed electrolytes such as cellulose, cellulose acetate, and cellulose acetate.

[0146] The present disclosure includes the following: <1> A two-dimensional particle having one or more layers, wherein the layers are represented by the following formula: M m X n(wherein M is at least one Group 3, 4, 5, 6 or 7 metal; X is a carbon atom, a nitrogen atom or a combination thereof; n is 1 or more and 4 or less; and m is greater than n and 5 or less), and a modified or terminal T (T is at least one selected from the group consisting of a hydroxyl group, a fluorine atom, a chlorine atom, an oxygen atom and a hydrogen atom) present on the surface of the layer body, the adsorbent being used for adsorbing a disease-causing substance. <2> The adsorbent according to <1>, wherein the disease-causing substance comprises a protein. <3> The adsorbent according to <1> or <2>, wherein the disease-causing substance comprises a uremic protein. <4> The adsorbent according to <3>, wherein the uremic protein comprises β2-microglobulin. <5> The adsorbent according to any one of <1> to <4>, wherein the disease-causing substance comprises a cytokine. <6> The adsorbent according to <5>, wherein the cytokine comprises at least one selected from the group consisting of interleukins, interferons, chemokines, hematopoietic factors, cell growth factors, and tumor necrosis factors. <7> The adsorbent according to any one of <1> to <6>, wherein the disease-causing substance comprises an electrolyte. <8> The electrolyte is Na + , K. + , Mg 2+ , Ca 2+ and P.O. 4 3- <9> An adsorbent according to <7>, comprising at least one selected from the group consisting of: <9> An adsorption sheet comprising the adsorbent according to any one of <1> to <8>. <10> A separation membrane comprising the adsorbent according to any one of <1> to <8>. <11> An artificial dialysis machine comprising the adsorbent according to any one of <1> to <8>. <12> A method for producing an adsorbent used to adsorb a disease-causing substance, comprising: (a) preparing a predetermined precursor, and (b) using an etching solution to remove at least a portion of A atoms from the precursor to obtain an etched product, and (c) washing the etched product to obtain an etched-washed product, and using the etched-washed product as two-dimensional particles to obtain an adsorbent.

[0147] 1a, 1b Layer body (M m X n layer) 3a, 5a, 3b, 5b Modified or terminal T 7a, 7b MXene layer 10a, 10b MXene particles (particles of layered material) 40 Hemodialysis device 41, 41A Blood inlet 42, 42A Blood outlet 43, 43A Blood pump 44, 44A Blood purification device 45, 45A Separation membrane 46, 46A Blood passage area of ​​blood purification device 47, 47A Dialysis fluid passage area of ​​blood purification device 48, 48A Unused dialysate tank 49, 49A Used dialysate tank 50, 50A Dialysis fluid pump 51 Semipermeable membrane

Claims

1. two-dimensional particles having one or more layers, The layer has the following formula: M m X n wherein M is at least one Group 3, 4, 5, 6, or 7 metal; X is a carbon atom, a nitrogen atom, or a combination thereof; n is 1 or more and 4 or less, m is greater than n and is equal to or less than 5. and a modification or terminal T (T is at least one selected from the group consisting of a hydroxyl group, a fluorine atom, a chlorine atom, an oxygen atom, and a hydrogen atom) present on the surface of the layer body, It is used to adsorb disease-causing substances, The disease-causing substance includes one or more selected from β2-microglobulin and electrolytes, The adsorbent, wherein the electrolyte comprises at least one selected from the group consisting of a + , K + , Mg 2+ , Ca 2+ and PO 4 3− .

2. The adsorbent of claim 1 , wherein the disease-causing substance comprises a protein.

3. The adsorbent of claim 1 , wherein the disease-causing substances include cytokines.

4. The adsorbent according to claim 3 , wherein the cytokine comprises at least one selected from the group consisting of interleukins, interferons, chemokines, hematopoietic factors, cell growth factors and tumor necrosis factors.

5. An adsorbent sheet comprising the adsorbent material according to any one of claims 1 to 4.

6. A separation membrane comprising the adsorbent according to any one of claims 1 to 4.

7. An artificial dialysis machine comprising the adsorbent according to any one of claims 1 to 4.

8. 1. A method for producing an adsorbent used for adsorbing disease-causing substances, comprising: (a) a compound of the formula: M m AX n (wherein M is at least one metal of Group 3, 4, 5, 6, 7, including at least Ti); X is a carbon atom, a nitrogen atom, or a combination thereof; A is at least one Group 12, 13, 14, 15, or 16 element; n is 1 or more and 4 or less, m is greater than n and is equal to or less than 5. providing a precursor represented by (b) removing at least a portion of the A atoms from the precursor using an etchant; Obtaining an etched product by the above-mentioned method. (c) cleaning the etched product to obtain an etch-cleaned product; Using the etching and cleaning treatment product as two-dimensional particles to obtain an adsorbent, The disease-causing substance includes one or more selected from β2-microglobulin and electrolytes, The method for producing an adsorbent, wherein the electrolyte comprises at least one selected from the group consisting of a + , K + , Mg 2+ , Ca 2+ and PO 4 3− .